Surface treatment compositions and methods

ABSTRACT

This disclosure relates to methods and compositions for treating a wafer having a pattern disposed on a surface of the wafer.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional ApplicationSer. No. 62/613,849, filed on Jan. 5, 2018, and U.S. ProvisionalApplication Ser. No. 62/649,685, filed on Mar. 29, 2018, which arehereby incorporated by reference in their entirety.

TECHNICAL FIELD

This disclosure relates generally to surface treatment, and moreparticularly to liquid treatment of semiconductor surfaces whereformation of a hydrophobic layer is desired.

BACKGROUND

At sub-20 nm critical dimensions, pattern collapse of FinFET's anddielectric stacks during wet clean and drying has become a major problemin semiconductor manufacturing processes. The conventional theory ofpattern collapse implicates high capillary forces during rinse and dryas major contributors leading to the collapse phenomenon. However, otherchemical and substrate properties may play an important role as well,namely, liquid surface tension and viscosity, substrate mechanicalstrength, pattern density and aspect ratio, and cleaner chemistry damageto substrate surfaces.

SUMMARY

It has been found that low surface tension modifying fluids that impartthe surfaces of a semiconductor substrate (e.g., a silicon or copperwafer) with a hydrophobic layer (e.g., a hydrophobic monolayer) canminimize the capillary forces that drive pattern collapse during adrying process. Without wishing to be bound by theory, it is believedthat the Laplace pressure is minimized when the contact angle, i.e., theangle a liquid (e.g., water) creates when in contact with a substratesurface, is at or near 90 degrees. This in combination with the presenceof a low surface tension fluid can greatly reduce the forces that causepattern collapse.

In general, this disclosure provides methods and compositions fortreating a patterned surface of a semiconductor substrate (e.g., apatterned wafer) where a hydrophobic layer is formed on the surface,thereby minimizing or preventing pattern collapse as the surface issubjected to typical cleaning and drying steps in a semiconductormanufacturing process. The methods disclosed herein employ compositionsthat form a hydrophobic layer on the surface such that the treatedsurface has a water contact angle of at least about 50 degrees.

In one aspect, this disclosure features methods for treating asemiconductor substrate having a pattern disposed on a surface of thewafer. Such methods can include contacting the surface with a surfacetreatment composition to form a surface treatment layer such that thesurface treatment layer has a water contact angle of at least about 50degrees. The surface treatment composition can include (e.g., comprise,consist of, or consist essentially of) at least one siloxane compoundand at least one additive. The at least one additive includes an acidhaving a pKa of at most 0 or an anhydride thereof. The pattern caninclude a feature having a dimension of at most about 20 nm.

In another aspect, this disclosure features surface treatmentcompositions that include (1) at least one siloxane compound in anamount of from about 0.1 wt % to about 99.9 wt % of the surfacetreatment composition; and (2) at least one additive including an acidhaving a pKa of at most 0 or an anhydride thereof and being in an amountof from about 0.1 wt % to about 10 wt % of the surface treatmentcomposition.

In another aspect, this disclosure features surface treatmentcompositions consisting of (1) at least one siloxane compound in anamount of from about 0.1 wt % to about 99.9 wt % of the surfacetreatment composition; (2) at least one additive including a compoundselected from the group consisting of sulfonic acids and sulfonicanhydrides and being in an amount of from about 0.1 wt % to about 10 wt% of the surface treatment composition; and (3) optionally, at least oneorganic solvent.

In another aspect, this disclosure features articles that include asemiconductor substrate, and a surface treatment composition supportedby the semiconductor substrate. The surface treatment composition caninclude at least one siloxane compound and at least one additive. The atleast one additive includes an acid having a pKa of at most 0 or ananhydride thereof.

In still another aspect, this disclosure features kits that include afirst container including at least one siloxane compound; and a secondcontainer including at least one additive. The at least one additive caninclude an acid having a pKa of at most 0 or an anhydride thereof.

Other features, objects, and advantages of the invention will beapparent from the description and the claims.

DETAILED DESCRIPTION

In some embodiments, this disclosure relates to surface treatmentmethods. Such methods can be performed, for example, by contacting thesurface (e.g., a surface that has patterns) of a substrate (e.g., asemiconductor substrate such as a silicon or copper wafer) with asurface treatment composition that includes at least one (e.g., two,three, or four) siloxane compound and at least one (e.g., two, three, orfour) additive including an acid having a pKa of at most 0 or ananhydride thereof. The pattern can include a feature having a dimensionof at most about 20 nm. In general, the surface treatment compositionforms a surface treatment layer (e.g., a hydrophobic monolayer) on thesurface such that the surface has a water contact angle of at leastabout 50 degrees.

In some embodiments, semiconductor substrates that can be treated by thesurface treatment compositions described herein are constructed ofsilicon, silicon germanium, silicon nitride, copper, Group III-Vcompounds such as GaAs, or any combination thereof. In some embodiments,the semiconductor substrate can be a silicon wafer, a copper wafer, asilicon dioxide wafer, a silicon nitride wafer, a silicon oxynitridewafer, a carbon doped silicon oxide wafer, a SiGe wafer, or a GaAswafer. The semiconductor substrates may additionally contain exposedintegrated circuit structures such as interconnect features (e.g., metallines and dielectric materials) on their surfaces. Metals and metalalloys used for interconnect features include, but are not limited to,aluminum, aluminum alloyed with copper, copper, titanium, tantalum,cobalt, nickel, silicon, polysilicon titanium nitride, tantalum nitride,tin, tungsten, SnAg, SnAg/Ni, CuNiSn, CuCoCu, and/or CoSn. Thesemiconductor substrate may also contain layers of interlayerdielectrics, silicon oxide, silicon nitride, titanium nitride, siliconcarbide, silicon oxide carbide, silicon oxide nitride, titanium oxide,and/or carbon doped silicon oxides.

In some embodiments, the semiconductor substrate surface to be treatedby the surface treatment compositions described herein includes featurescontaining SiO₂, SiN, TiN, SiOC, SiON, Si, SiGe, Ge, and/or W. In someembodiments, the substrate semiconductor surface includes featurescontaining SiO₂ and/or SiN.

In general, the semiconductor substrate surface to be treated by thesurface treatment compositions described herein includes patterns formedby a prior semiconductor manufacturing process (e.g., a lithographicprocess including applying a photoresist layer, exposing the photoresistlayer to an actinic radiation, developing the photoresist layer, etchingthe semiconductor substrate beneath the photoresist layer, and/orremoving the photoresist layer). In some embodiments, the patterns caninclude features having at least one (e.g., two or three) dimension(e.g., a length, a width, and/or a depth) of at most about 20 nm (e.g.,at most about 15 nm, at most about 10 nm, or at most about 5 nm) and/orat least about 1 nm (e.g., at least about 2 nm or at least about 5 nm).

In general, the surface treatment compositions described herein caninclude at least one (two, three, or four) siloxane compound and atleast one (e.g., two, three, or four) additive. A siloxane compound canbe a disiloxane, an oligosiloxane, a cyclosilxoane, or a polysiloxane.As used herein, the term “oligosiloxane” refers to a compound having 3-6siloxane units, and the term “polysiloxane” refers to a compound havingmore than 6 siloxane units.

Examples of suitable siloxane compounds that can be used in the surfacetreatment compositions described herein include hexamethyldisiloxane,1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane,1,1,1-triethyl-3,3-dimethyldisiloxane,1,1,3,3-tetra-n-octyldimethyldisiloxane,bis(nonafluorohexyl)tetramethyldisiloxane,1,3-bis(trifluoropropyl)tetramethyldisiloxane,1,3-di-n-butyltetramethyldisiloxane,1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane,1,3-diphenyltetramethyl-disiloxane, hexa-n-butyldisiloxane,hexaethyldisiloxane, hexavinyldisiloxane,1,1,1,3,3-pentamethyl-3-acetoxydisiloxane,1-allyl-1,1,3,3-tetramethyldisiloxane,1,3-bis(3-aminopropyl)tetramethyldisiloxane,1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)-tetramethyldisiloxane,1,3-divinyltetraphenyldisiloxane, 1,3-divinyltetramethyl-di siloxane,1,3-diallyltetrakis(trimethylsiloxy)disiloxane,1,3-diallyltetramethyl-di siloxane,1,3-diphenyltetrakis(dimethylsiloxy)disiloxane,(3-chloropropyl)pentamethyl-di siloxane,1,3-divinyltetrakis(trimethylsiloxy)disiloxane,1,1,3,3-tetraisopropyl-di siloxane,1,1,3,3-tetravinyldimethyldisiloxane,1,1,3,3-tetracyclopentyldichloro-di siloxane,vinylpentamethyldisiloxane,1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane,1,3-bis[(bicyclo[2.2.1]hept-2-enyl)ethyl]tetramethyldisiloxane,1,1,1-triethyl-3,3,3-trimethyldisiloxane,1,3-bis(3-methacryloxypropyl)tetramethyl-di siloxane,1,3-bis(chloromethyl)tetramethyldisiloxane,1,1,3,3-tetramethyl-1,3-diethoxydisiloxane,1,1,3,3-tetraphenyldimethyldisiloxane, methacryloxypentamethyl-disiloxane, pentamethyldisiloxane,1,3-bis(3-chloropropyl)tetramethyldisiloxane,1,3-bis(4-hydroxybutyl)tetramethyldisiloxane,1,3-bis(triethoxysilylethyl)tetramethyl-di siloxane,3-aminopropylpentamethyldisiloxane,1,3-bis(2-aminoethylaminomethyl)-tetramethyldisiloxane,1,3-bis(3-carboxypropyl)tetramethyldisiloxane,1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane,1,3-diethynyltetramethyldisiloxane,n-butyl-1,1,3,3-tetramethyldisiloxane,1,3-dichlorotetraphenyldisiloxane, 1,3-dichlorotetramethyl-di siloxane,1,3-di-t-butyldisiloxane, 1,3-dimethyltetramethoxydisiloxane,1,3-divinyltetraethoxydisiloxane,1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane,vinyl-1,1,3,3-tetramethyldisiloxane,platinum-[1,3-bis(cyclohexyl)imidazol-2-ylidene hexachlorodisiloxane,1,1,3,3-tetraisopropyl-1-chlorodisiloxane,1,1,1-trimethyl-3,3,3-triphenyldisiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane,3,3-diphenyl-tetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane,hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane,1,5-diethoxyhexamethyltrisiloxane, 3-ethylheptamethyl-trisiloxane,3-(tetrahydrofurfuryloxypropyl)heptamethyltrisiloxane,3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane,1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane,1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane,hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane,octachlorotrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane,(3,3,3-trifluoropropyl)methylcyclotrisiloxane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,3-(3-acetoxypropyl)heptamethyltrisiloxane,3-(m-pentadecylphenoxypropyl)heptamethyltrisiloxane,limonenyltrisiloxane, 3-dodecylheptamethyltrisiloxane,3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane,1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane,1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane,1,5-dichlorohexamethyltrisiloxane, 3-triacontylheptamethyltrisiloxane,3-(3-hydroxypropyl)heptamethyltrisiloxane,hexamethylcyclomethylphosphonoxytrisiloxane,3-octadecylheptamethyltrisiloxane, furfuryloxytrisiloxane,tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane,a diphenyl siloxane-dimethylsiloxane copolymer,1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, adimethylsiloxane-[65-70%(60% propylene oxide/40% ethylene oxide)] blockcopolymer, bis(hydroxypropyl)tetramethyldisiloxane,tetra-n-propyltetramethylcyclotetrasiloxane,octaethylcyclotetrasiloxane, decamethyltetrasiloxane,dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane,tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane,polydimethylsiloxane, polyoctadecylmethylsiloxane, hexacosyl terminatedpolydimethylsiloxane, decamethylcyclopentasiloxane,poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy terminatedpolydimethylsiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, andtriethylsiloxy terminated polydiethylsiloxane.

In some embodiments, the at least one siloxane compound can be from atleast about 0.1 wt % (e.g., at least about 1 wt %, at least about 5 wt%, at least about 10 wt %, at least about 20 wt %, at least about 30 wt%, at least about 40 wt %, at least about 50 wt %, at least about 60 wt%, at least about 70 wt %, at least about 80 wt %, at least about 90 wt%, at least about 95 wt %, at least about 97 wt %, or at least about 99wt %) to at most about 99.9 wt % (e.g., at most about 99 wt %, at mostabout 98 wt %, at most about 96 wt %, at most about 94 wt %, at mostabout 92 wt %, at most about 90 wt %, at most about 85 wt %, at mostabout 80 wt %, at most about 75 wt %, at most about 70 wt %, at mostabout 65 wt %, at most about 60 wt %, at most about 55 wt %, or at mostabout 55 wt %) of the surface treatment compositions described herein.

In some embodiments, the additives contemplated for use in the surfacetreatment compositions described herein can include an acid having a pKaof at most 0 or an anhydride thereof. Examples of such acids or theiranhydrides include methanesulfonic acid, trifluoromethanesulfonic acid,methanesulfonic anhydride, trifluoromethanesulfonic anhydride,perchloric acid, nitric acid, sulfuric acid, toluenesulfonic acid,dodecylbenzenesulfonic acid, hydroiodic acid, hydrobromic acid,hydrochloric acid, chloric acid, trichloroacetic acid, trifluoroaceticacid, and fluorosulfuric acid. In some embodiments, the at least oneadditive can further include a second additive (e.g., an acid having apKa of at least 0 or an anhydride thereof) different from an acid havinga pKa of at most 0. An example of such a second additive is aceticanhydride.

In some embodiments, the at least one additive can be from at leastabout 0.1 wt % (e.g., at least about 0.5 wt %, at least about 1 wt %, atleast about 1.5 wt %, at least about 2 wt %, at least about 2.5 wt %, atleast about 3 wt %, at least about 3.5 wt %, at least about 4 wt %, atleast about 4.5 wt %, or at least about 5 wt %) to at most about 10 wt %(e.g., at most about 9 wt %, at most about 8 wt %, at most about 7 wt %,at most about 6 wt %, at most about 5 wt %, at most about 4 wt %, or atmost about 3 wt %) of the surface treatment compositions describedherein.

Without wishing to be bound by theory, it is believed that, during useof the surface treatment compositions, the additive (e.g., a strongacid) can react with the siloxane compound to form a silylated compound,which can facilitate the formation of a hydrophobic siloxane unit ontothe surface to be treated, which in turn can minimize the capillaryforces that drive pattern collapse during a rinsing or drying process.

In some embodiments, the surface treatment compositions described hereincan further include at least one organic solvent, such as anhydrides,glycol ethers, glycol ether acetates, alkanes, aromatic hydrocarbons,sulfones, sulfoxides, ketones, aldehydes, esters, lactams, lactones,acetals, hemiacetals, alcohols, carboxylic acids (e.g., those having apKa of at least 0) and ethers. Examples of suitable solvents includeacetic anhydride, propylene glycol methyl ether acetate, a C₆-C₁₆alkane, toluene, xylene, mesitylene, tetraethylene glycol dimethylether, propylene glycol dimethyl ether, ethylene glycol dimethyl ether,dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether,dipropylene glycol dibutylether, n-dibutyl ether, dimethylsulfone,sulfolane, benzyl alcohol, t-butyl alcohol, t-amyl alcohol, methyl ethylketone, acetic acid, and isobutyl methyl ketone. In some embodiments,the surface treatment compositions described herein can be substantiallyfree of an organic solvent.

In some embodiments, the at least one organic solvent can be from atleast about 3 wt % (e.g., at least about 5 wt %, at least about 10 wt %,at least about 20 wt %, at least about 30 wt %, at least about 40 wt %,at least about 50 wt %, at least about 60 wt %, at least about 70 wt %,at least about 80 wt %, or at least about 90 wt %) to at most about 95wt % (e.g., at most about 85 wt %, at most about 75 wt %, at most about65 wt %, at most about 55 wt %, at most about 45 wt %, at most about 35wt %, or at most about 25 wt %) of the surface treatment compositionsdescribed herein.

In some embodiments, the surface treatment compositions described hereincan include only three types of components, i.e., (1) at least onesiloxane compound, (2) at least one additive, and (3) at least oneorganic solvent. In some embodiments, the at least one organic solventis optional and can be omitted from the surface treatment compositionsdescribed herein. In some embodiments, the surface treatmentcompositions described herein can be substantially free of a solvent(such as water or an organic solvent). As used herein, the term“substantially free” refers to the weight % of a component being at mostabout 0.1% (e.g., at most about 0.05%, at most about 0.01%, at mostabout 0.005%, at most about 0.001%, or at about 0%).

Without wishing to be bound by theory, it is believed that the surfacetreatment composition can form a surface treatment layer (e.g., ahydrophobic layer such as a hydrophobic monolayer) on a patternedsurface of a semiconductor substrate such that the patterned surface hasa water contact angle of at least about 50 degrees (e.g., at least about55 degrees, at least about 60 degrees, at least about 65 degrees, atleast about 70 degrees, at least about 75 degrees, at least about 80degrees, at least about 85 degrees, at least about 89 degrees, at leastabout 90 degrees, at least about 95 degrees, or at least about 100degrees). Without wishing to be bound by theory, it is believed thatsuch a surface treatment layer can prevent or minimize the collapse ofthe patterned features (e.g., having a dimension of at most about 20 nm)on the semiconductor substrate during a drying step typically used inthe semiconductor manufacturing process.

In some embodiments, the surface treatment compositions described hereincan specifically exclude one or more of the additive components, in anycombination, if more than one. Such components are selected from thegroup consisting of non-aromatic hydrocarbons, silazanes (e.g., cyclicsilazanes or heterocyclic silazanes), protic solvents (e.g., alcohols oramides), lactones (e.g., those with 5- or 6-membered rings), certainSi-containing compounds (e.g., those having a Si—H group or anaminosilyl group), polymers, oxygen scavengers, quaternary ammoniumsalts including quaternary ammonium hydroxides, amines, bases (such asalkaline bases (e.g., NaOH, KOH, LiOH, Mg(OH)₂, and Ca(OH)₂)),surfactants, defoamers, fluoride-containing compounds (e.g., HF, H₂SiF₆,H₂PF₆, HBF₄, NH₄F, and tetraalkylammonium fluoride), oxidizing agents(e.g., peroxides, hydrogen peroxide, ferric nitrate, potassium iodate,potassium permanganate, nitric acid, ammonium chlorite, ammoniumchlorate, ammonium iodate, ammonium perborate, ammonium perchlorate,ammonium periodate, ammonium persulfate, tetramethylammonium chlorite,tetramethylammonium chlorate, tetramethylammonium iodate,tetramethylammonium perborate, tetramethylammonium perchlorate,tetramethylammonium periodate, tetramethylammonium persulfate, ureahydrogen peroxide, and peracetic acid), abrasives, silicates,hydroxycarboxylic acids, carboxylic and polycarboxylic acids lackingamino groups, silanes (e.g., alkoxysilanes), cyclic compounds (e.g.,cyclic compounds containing at least two rings, such as substituted orunsubstituted naphthalenes, or substituted or unsubstitutedbiphenylethers) other than the cyclosiloxanes described herein,chelating agents (e.g., azoles, diazoles, triazoles, or tetrazoles),corrosion inhibitors (such as azole or non-azole corrosion inhibitors),buffering agents, guanidine, guanidine salts, pyrrolidone, polyvinylpyrrolidone, metal halides, and metal-containing catalysts.

In some embodiments, the surface treatment methods described herein canfurther include contacting the surface of a substrate with at least oneaqueous cleaning solution before contacting the surface with a surfacetreatment composition. In such embodiments, the at least one aqueouscleaning solution can include water, an alcohol, aqueous ammoniumhydroxide, aqueous hydrochloric acid, aqueous hydrogen peroxide, anorganic solvent, or a combination thereof.

In some embodiments, the surface treatment methods described herein canfurther include contacting the surface of a substrate with a firstrinsing solution (e.g., water, an organic solvent such as isopropanol,or a combination thereof) after contacting the surface with the at leastone aqueous cleaning solution but before contacting the surface with thesurface treatment composition. In some embodiments, the surfacetreatment methods described herein can further include contacting thesurface with a second rinsing solution (e.g., water, an organic solventsuch as isopropanol, or a combination thereof) after contacting thesurface with the surface treatment composition. In some embodiments, thesurface treatment methods described herein can further include dryingthe surface (e.g., after contacting the surface with first rinsingsolution, the surface treatment composition, or the second rinsingsolution). In some embodiments, the surface treatment methods describedherein can further include removing the surface treatment layer from thesurface.

In some embodiments, this disclosure provides methods for cleaning asemiconductor substrate (e.g., a wafer) having a pattern disposed on asurface of the substrate. Such methods can be performed, for example,by:

a) optionally, contacting the surface with an aqueous cleaning solution;

b) optionally, contacting the surface with a first rinsing solution;

c) contacting the surface with a surface treatment composition, whereinthe surface treatment composition includes at least one siloxanecompound and at least one additive, in which the at least one additiveincludes an acid having a pKa of at most 0 or an anhydride thereof, andthe surface treatment composition forms a surface treatment layer on thesurface such that the surface has a water contact angle of at leastabout 50 degrees;

d) optionally, contacting the surface with a second rinsing solution;

e) drying the surface; and

f) optionally, removing the surface treatment layer to form a cleaned,patterned surface.

In such embodiments, the pattern can include a feature having adimension of at most about 20 nm.

In step a) of the above described methods, the substrate (e.g., a wafer)bearing a patterned surface can optionally be treated with one or moreaqueous cleaning solutions. When the patterned surface is treated withtwo or more aqueous cleaning solutions, the cleaning solutions can beapplied sequentially. The aqueous cleaning solutions can be water aloneor can be solutions containing water, a solute, and optionally anorganic solvent. In some embodiments, the aqueous cleaning solutions caninclude water, an alcohol (e.g., a water soluble alcohol such asisopropanol), an aqueous ammonium hydroxide solution, an aqueoushydrochloric acid solution, an aqueous hydrogen peroxide solution, anorganic solvent (e.g., a water soluble organic solvent), or acombination thereof.

In step b), the cleaning solution from step a) can be optionally rinsedaway using a first rinsing solution. The first rinsing solution caninclude water, an organic solvent (e.g., isopropanol), or an aqueoussolution containing an organic solvent. In some embodiments, the firstrinsing solution is at least partially miscible with the cleaningsolution used in step a). In some embodiments, step b) can be omittedwhen the cleaning solution used in step a) is not moisture sensitive ordoes not contain any appreciable amount of water.

In step c), the substrate surface can be treated with a surfacetreatment composition of the disclosure described above to form amodified surface having a surface treatment layer (e.g., a hydrophobiclayer). The modified surface thus formed can be hydrophobic and can havea water contact angle of at least about 50 degrees. In some embodiments,the contact angle can be at least about 55 degrees (e.g., at least about60 degrees, at least about 65 degrees, at least about 70 degrees, atleast about 75 degrees, at least about 80 degrees, at least about 85degrees, at least about 90 degrees, at least about 95 degrees, or atleast about 100 degrees) and/or at most about 180 degrees (e.g., at mostabout 170 degrees, at most about 160 degrees, or at most about 150degrees). In some embodiments, this step can be performed at atemperature of about 20-35° C. for a process time ranging from about 10seconds to about 300 seconds.

In step d), after the substrate surface is treated with a surfacetreatment composition, the surface can be rinsed with a second rinsingsolution. The second rinsing solution can include water, an organicsolvent (e.g., isopropanol), or an aqueous solution containing anorganic solvent. In some embodiments, this step can be performed at atemperature of about 20-70° C.

In step e), the substrate surface can be dried (e.g., by using apressurized gas). Without wishing to be bound by theory, it is believedthat, after the substrate surface is treated with a surface treatmentcomposition described herein, the collapse of patterns on the surfaceduring this drying step is minimized.

In step f), after the drying step, the surface treatment layer (e.g., ahydrophobic layer) can optionally be removed. In general, the surfacetreatment layer can be removed by a number of methods depending on thechemical characteristics of the modified surface. Suitable methods forremoving the surface treatment layer include plasma sputtering; plasmaashing; thermal treatment at atmospheric or sub atmospheric pressure;treatment with an acid, base, oxidizing agent or solvent containingcondensed fluid (e.g., supercritical fluids such as supercritical CO₂);vapor or liquid treatment; UV irradiation; or combinations thereof.

The semiconductor substrate having a cleaned, patterned surface preparedby the method described above can be further processed to form one ormore circuits on the substrate or can be processed to form into asemiconductor device (e.g., an integrated circuit device such as asemiconductor chip) by, for example, assembling (e.g., dicing andbonding) and packaging (e.g., chip sealing).

In some embodiments, this disclosure features articles (e.g., anintermediate semiconductor article formed during the manufacturing of asemiconductor device) that includes a semiconductor substrate, and asurface treatment composition described herein supported by thesemiconductor substrate. The surface treatment composition can includeat least one siloxane compound and at least one additive comprising anacid having a pKa of at most 0 or an anhydride thereof, such as thosedescribed above.

In some embodiments, this disclosure features kits that include a firstcontainer including at least one siloxane compound described above; anda second container including at least one additive described above. Ifdesired, the first or second container can further include at least oneorganic solvent to form a solution with the components in eachcontainer. In some embodiments, the components in the first and secondcontainers can be mixed to form a surface treatment composition at thepoint of use right before applying the surface treatment composition toa surface of a semiconductor substrate. Without wishing to be bound bytheory, it is believed that such a method is particularly suitable for asurface treatment composition having a relatively short shelf life. Inembodiments where a surface treatment composition has a relatively longshelf life, the components in the first and second containers can bemixed to form one solution, which can be stored for a relative longperiod of time before use.

The present disclosure is illustrated in more detail with reference tothe following examples, which are for illustrative purposes and shouldnot be construed as limiting the scope of the present disclosure.

Example 1

Surface Treatment Solutions (i.e., formulations 1-20) were prepared bymixing the components at room temperature. The compositions offormulations 1-20 are summarized in Table 1 below. All percentageslisted in Table 1 are weight percentages, unless indicated otherwise.

The Coupons containing SiO₂ films on Si substrates were cut into 1×1inch squares. The coupons were immersed vertically into 100 mL ofstirred (50 RPM) Surface Treatment Solutions and were kept at roomtemperature for 30 seconds. The coupons were then rinsed withisopropanol at 50° C. for 60 seconds and dried by using pressurizednitrogen gas.

The coupons were placed on the AST VCA 3000 Contact Angle Tool and thefollowing procedure was followed to measure the contact angles:

1. Place the SiO₂ coupon onto the stage.

2. Raise the stage upward by rotating Vertical Knob clockwise until thespecimen is just below the needle.

3. Dispense a drop of De-ionized water, lightly touching the specimensurface, then lower the specimen until the droplet separates from theneedle tip.

4. Center the drop across the field-of-view using transverse knob forstage adjustment.

5. Focus the drop in field-of-view to get a sharp image by moving thestage along guide rails.

6. Click the “AutoFAST” button to freeze the image and calculate. Twonumbers will be displayed; these are the left and right contact angles.

7. To calculate manually, use the mouse to place five markers around thedroplet.

8. Select the droplet icon from the Main Menu to calculate the contactangle.

9. This will create a curve fit and tangent lines on the image. Twonumbers will be displayed in the left-hand-corner of the screen; theseare the left and right contact angles.

10. Repeat above procedure at 3 substrate sites and average theresulting contact angles and report the average result in Table 1.

TABLE 1 Form. # Siloxane Solvent(s) Additives SiO₂ CA¹ 1 5% HMDSO² 43.5%PGMEA³ 1.5% Triflic acid 82.6 50% n-Decane 2 95.5% HMDSO — 1.5% Triflicacid 89.30 3% Acetic anhydride 3 88.5% HMDSO 10% Acetic Anhydride 1.5%Triflic acid 86.2 4 68.5% HMDSO 30% Acetic Anhydride 1.5% Triflic acid87.8 5 48.5% HMDSO 50% Acetic Anhydride 1.5% Triflic acid 87.7 6 97%HMDSO — 3% Triflic acid 95.8 7 97% HMDSO — 3% Methane sulfonic 86.8 acid8 99% HMDSO — 1% Triflic acid 95.5 9 95% HMDSO — 5% Triflic acid 95.8 1072% HMDSO 25% Xylene 3% Triflic acid 93.9 11 47% HMDSO 50% Xylene 3%Triflic acid 93.9 12 97% HMDSO — 3% Methane sulfonic 80.8 anhydride 1397% HMDSO — 3% Trifluoromethane 94.3 sulfonic anhydride 14 47% HMDSO 50%n-Decane 3% Methane sulfonic 71.7 anhydride 15 47% HMDSO 50% n-Decane 3%Methane sulfonic 77.6 acid 16 47% HMDSO 50% n-Decane 3% Trifluoromethane98.4 sulfonic anhydride 17 47% HMDSO 50% Isopar G 3% Trifluoromethane98.1 sulfonic anhydride 18 47% HMDSO 50% Isopar H 3% Trifluoromethane99.4 sulfonic anhydride 19 47% HMDSO 50% Isopar P 3% Trifluoromethane100.9 sulfonic anhydride 20 47% HMDSO 50% Solvesso 200ND 3%Trifluoromethane 100 sulfonic anhydride ¹“CA” refers to contact angle(degrees) ²“HMDSO” refers to hexamethyldisiloxane ³ “PGMEA” refers topropylene glycol methyl ether acetate

As shown in Table 1, all of formulations 1-20 (which contained asiloxane, a strong acid, and optionally an aprotic solvent) exhibitedrelatively large contact angles on a SiO₂ surface.

Example 2

Surface treatment solutions (i.e., formulations 21-56) were prepared bymixing the components at room temperature. The compositions offormulations 21-56 are summarized in Table 2 below. All percentageslisted in Table 2 are weight percentages, unless indicated otherwise.

The contact angle results in Table 2 were obtained using the same methodoutlined in Example 1.

The silicon pillar collapse test results in Table 2 were obtained usingthe following procedures: Patterned wafers were treated withformulations 21-56. Si pillar (with an aspect ratio of 22) patternedwafers were diced into 0.5 inch by 0.5 inch coupons. The coupons werethen immersed into stirred 25° C. surface treatment solutions for 180seconds. The coupons were removed from the surface treatment solutions,rinsed in a beaker containing isopropyl at room temperature for 30seconds, and rinsed in a beaker containing stirred 50° C. isopropylalcohol for 60 seconds. The coupons were then removed from the isopropylalcohol rinse and dried with a N2 gas dispense gun orientedperpendicularly to the coupon at a working distance of 1 inch with gaspressure of 45 psi. The coupons were then analyzed by scanning electronmicroscopy over three randomly selected sites at a magnification of50000× and the number of non-collapsed silicon pillars were tabulated.The average of non-collapsed Si-pillars at the three sites are reportedin Table 2 as a percentage of the total Si pillars observed.

TABLE 2 Non-Collapsed Form. # Siloxane Solvent(s) Additives SiO₂ CA¹ SiPillars 21 10% HMDSO² 87% Acetic acid 3% Triflic acid — 96.6% 22 20%HMDSO 77% Acetic acid 3% Triflic acid — 99.0% 23 10% HMDSO 40% Aceticacid 3% Triflic acid — 97.9% 47% Tetraglyme³ 24 20% HMDSO 40% Aceticacid 3% Triflic acid — 98.8% 37% Tetraglyme 25 16.6% HMDSO 80.4% Aceticacid 3% Triflic acid — 87.8% 26 13.3% HMDSO 83.7% Acetic acid 3% Triflicacid — 98.3% 27 16.6% HMDSO 80.9% Acetic acid 2.5% Triflic acid — 96.2%28 13.3% HMDSO 84.2% Acetic acid 2.5% Triflic acid — 94.3% 29 16.6%HMDSO 81.4% Acetic acid 2% Triflic acid — 98.8% 30 13.3% HMDSO 84.7%Acetic acid 2% Triflic acid —  99% 31 13.3% HMDSO 83.7% Acetic acid 2%Triflic acid — 97.8% 1% Acetic anhydride 32 7.5% HMDSO 89.5% Acetic acid3% Triflic acid — 98.6% 33 5% HMDSO 92% Acetic acid 3% Triflic acid —97.1% 34 13.3% HMDSO 84.7% Acetic acid 2% Triflic acid — 98.3% 35 13.3%HMDSO 85.7% Acetic acid 1% Triflic acid — 94.1% 36 10% HMDSO 88% Aceticacid 2% Triflic acid 93.4 99.7% 37 10% HMDSO 87% Acetic acid 2% Triflicacid 92.5 99.2% 1% Acetic anhydride 38 10% HMDSO 90% Acetic acid — 42.8— 39 10% HMDSO 89% Acetic acid 1% Acetic anhydride 48.7 — 40 10% HMDSO88% Acetic anhydride 2% Triflic acid 92.7  ~50% 41 10% HMDSO 88% Aceticacid 2% Trifluoroacetic acid 40.8 — 42 10% HMDSO 87% Acetic acid 1%Acetic anhydride 42.1 — 2% Trifluoroacetic acid 43 10% HMDSO 79% Aceticacid 1% Acetic anhydride 91.2  <10% 10% Methanesulfonic acid 44 10%HMDSO 77% Acetic acid 1% Acetic anhydride 93.6  <10% 10% Methanesulfonicacid 45 13.3% HMDSO 86.2% Acetic acid 0.5% Triflic acid — 96.6% 46 13.3%HMDSO 86.5% Acetic acid 0.2% Triflic acid — 96.6% 47 5% HMDSO 93% Aceticacid 2% Triflic acid — 94.2% 48 7.5% HMDSO 90.5% Acetic acid 2% Triflicacid — 96.2% 49 1% HMDSO 96% Acetic acid 2% Triflic acid — 93.4% 1%Acetic anhydride 50 5% HMDSO 92% Acetic acid 2% Triflic acid — 99.0% 1%Acetic anhydride 51 13.3% HMDSO 82.7% Acetic acid 2% Triflic acid —98.4% 1% Acetic anhydride 1% Triflic anhydride 52 1% HMDSO 95% Aceticacid 2% Triflic acid — 98.8% 1% Acetic anhydride 1% Triflic anhydride 5313.3% HMDSO 83.7% Acetic acid 2% Triflic acid — 98.6% 1% Triflicanhydride 54 13.3% HMDSO 83.1% Acetic acid 2% Triflic acid — 97.7% 1.6%Triflic anhydride 55 13.3% HMDSO 84.7% Acetic acid 1.69% Triflic acid —93.4% 0.31% Triflic anhydride 56 13.3% HMDSO 84.7% Acetic acid 0.4%Triflic acid — 93.6% 1.6% Triflic anhydride ¹“CA” refers to contactangle (degrees) ²“HMDSO” refers to hexamethyldisiloxane ³“Tetraglyme”refers to tetraethylene glycol dimethyl ether

As shown in Table 2, upon treatment with formulations 21-37 and 45-56, asubstantial portion of silicon pillars on patterned silicon wafersremained after a cleaning or drying process. In addition, formulations36 and 37 exhibited relatively large contact angles on a SiO₂ surface.By contrast, formulations 38 and 39 (which did not contain an acidhaving a pKa less than 0) exhibited relatively small contact angles on aSiO₂ surface.

Other embodiments are within the scope of the following claims.

What is claimed is:
 1. A method for treating a semiconductor substratehaving a pattern disposed on a surface of the wafer, comprising:contacting the surface with a surface treatment composition to form asurface treatment layer such that the surface treatment layer has awater contact angle of at least about 50 degrees, the surface treatmentcomposition comprising at least one siloxane compound and at least oneadditive comprising an acid having a pKa of at most 0 or an anhydridethereof; wherein the pattern comprises a feature having a dimension ofat most about 20 nm.
 2. The method of claim 1, wherein the at least onesiloxane compound comprises a disiloxane, an oligosiloxane, acyclosilxoane, or a polysiloxane.
 3. The method of claim 2, wherein theat least one siloxane compound comprises hexamethyldisiloxane,1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane,1,1,1-triethyl-3,3-dimethyldisiloxane,1,1,3,3-tetra-n-octyldimethyldisiloxane,bis(nonafluorohexyl)tetramethyldisiloxane,1,3-bis(trifluoropropyl)tetramethyldisiloxane,1,3-di-n-butyltetramethyldisiloxane,1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane,1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane,hexaethyldisiloxane, hexavinyldisiloxane,1,1,1,3,3-pentamethyl-3-acetoxydisiloxane,1-allyl-1,1,3,3-tetramethyldisiloxane,1,3-bis(3-aminopropyl)tetramethyldisiloxane,1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,1,3-divinyltetraphenyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-diallyltetrakis(trimethylsiloxy)disiloxane,1,3-diallyltetramethyldisiloxane,1,3-diphenyltetrakis(dimethylsiloxy)disiloxane,(3-chloropropyl)pentamethyldisiloxane,1,3-divinyltetrakis(trimethylsiloxy)disiloxane,1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane,1,1,3,3-tetracyclopentyldichlorodisiloxane, vinylpentamethyldisiloxane,1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane,1,3-bis[(bicyclo[2.2.1]hept-2-enyl)ethyl]tetramethyldisiloxane,1,1,1-triethyl-3,3,3-trimethyldisiloxane,1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane,1,3-bis(chloromethyl)tetramethyldisiloxane,1,1,3,3-tetramethyl-1,3-diethoxydisiloxane,1,1,3,3-tetraphenyldimethyldisiloxane,methacryloxypentamethyldisiloxane, pentamethyldisiloxane,1,3-bis(3-chloropropyl)tetramethyldisiloxane,1,3-bis(4-hydroxybutyl)tetramethyldisiloxane,1,3-bis(triethoxysilylethyl)tetramethyldisiloxane,3-aminopropylpentamethyldisiloxane,1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane,1,3-bis(3-carboxypropyl)tetramethyldisiloxane,1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane,1,3-diethynyltetramethyldisiloxane,n-butyl-1,1,3,3-tetramethyldisiloxane,1,3-dichlorotetraphenyldisiloxane, 1,3-dichlorotetramethyldisiloxane,1,3-di-t-butyldisiloxane, 1,3-dimethyltetramethoxydisiloxane,1,3-divinyltetraethoxydisiloxane,1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane,vinyl-1,1,3,3-tetramethyldisiloxane,platinum-[1,3-bis(cyclohexyl)imidazol-2-ylidene hexachlorodisiloxane,1,1,3,3-tetraisopropyl-1-chlorodisiloxane,1,1,1-trimethyl-3,3,3-triphenyldisiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane,3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane,hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane,1,5-diethoxyhexamethyltrisiloxane, 3-ethylheptamethyltrisiloxane,3-(tetrahydrofurfuryloxypropyl)heptamethyltrisiloxane,3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane,1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane,1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane,hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane,octachlorotrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane,(3,3,3-trifluoropropyl)methylcyclotrisiloxane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,3-(3-acetoxypropyl)heptamethyltrisiloxane,3-(m-pentadecylphenoxypropyl)heptamethyltrisiloxane,limonenyltrisiloxane, 3-dodecylheptamethyltrisiloxane,3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane,1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane,1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane,1,5-dichlorohexamethyltrisiloxane, 3-triacontylheptamethyltrisiloxane,3-(3-hydroxypropyl)heptamethyltrisiloxane,hexamethylcyclomethylphosphonoxytrisiloxane,3-octadecylheptamethyltrisiloxane, furfuryloxytrisiloxane,tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane,a diphenyl siloxane-dimethylsiloxane copolymer,1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, adimethylsiloxane-[65-70%(60% propylene oxide/40% ethylene oxide)] blockcopolymer, bis(hydroxypropyl)tetramethyldisiloxane,tetra-n-propyltetramethylcyclotetrasiloxane,octaethylcyclotetrasiloxane, decamethyltetrasiloxane,dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane,tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane,polydimethylsiloxane, polyoctadecylmethylsiloxane, hexacosyl terminatedpolydimethylsiloxane, decamethylcyclopentasiloxane,poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy terminatedpolydimethylsiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, ortriethylsiloxy terminated polydiethylsiloxane.
 4. The method of claim 1,wherein the at least one siloxane compound is from about 0.1 wt % toabout 99.9 wt % of the surface treatment composition.
 5. The method ofclaim 1, wherein the at least one additive comprises methanesulfonicacid, trifluoromethanesulfonic acid, methanesulfonic anhydride,trifluoromethanesulfonic anhydride, acetic anhydride, perchloric acid,nitric acid, sulfuric acid, toluenesulfonic acid, dodecylbenzenesulfonicacid, hydroiodic acid, hydrobromic acid, hydrochloric acid, chloricacid, trichloroacetic acid, trifluoroacetic acid, or fluorosulfuricacid.
 6. The method of claim 1, wherein the at least one additive isfrom about 0.1 wt % to about 10 wt % of the surface treatmentcomposition.
 7. The method of claim 1, wherein the surface treatmentcomposition further comprises at least one organic solvent.
 8. Themethod of claim 7, wherein the at least one organic solvent is selectedfrom the group consist of anhydrides, glycol ethers, glycol etheracetates, alkanes, aromatic hydrocarbons, sulfones, sulfoxides, ketones,aldehydes, esters, lactams, lactones, acetals, hemiacetals, alcohols,carboxylic acids, and ethers.
 9. The method of claim 7, wherein the atleast one organic solvent comprises acetic anhydride, propylene glycolmethyl ether acetate, a C₆-C₁₆ alkane, toluene, xylene, mesitylene,tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether,ethylene glycol dimethyl ether, dipropylene glycol dimethyl ether,diethylene glycol dimethyl ether, dipropylene glycol dibutyl ether,n-dibutyl ether, dimethylsulfone, sulfolane, benzyl alcohol, t-butylalcohol, t-amyl alcohol, methyl ethyl ketone, acetic acid, or isobutylmethyl ketone.
 10. The method of claim 7, wherein the at least oneorganic solvent is from about 3 wt % to about 95 wt % of the surfacetreatment composition.
 11. The method of claim 1, wherein the surfacetreatment composition is substantially free of water.
 12. The method ofclaim 1, wherein the surface treatment composition consists of the atleast one siloxane compound, the at least one additive, and optionally,at least one organic solvent.
 13. The method of claim 1, furthercomprising contacting the surface with at least one aqueous cleaningsolution before contacting the surface with the surface treatmentcomposition.
 14. The method of claim 13, wherein the at least oneaqueous cleaning solution comprise water, an alcohol, aqueous ammoniumhydroxide, aqueous hydrochloric acid, aqueous hydrogen peroxide, anorganic solvent, or a combination thereof.
 15. The method of claim 13,further comprising contacting the surface with a first rinsing solutionafter contacting the surface with the at least one aqueous cleaningsolution but before contacting the surface with the surface treatmentcomposition.
 16. The method of claim 15, further comprising contactingthe surface with a second rinsing solution after contacting the surfacewith the surface treatment composition.
 17. The method of claim 1,further comprising drying the surface.
 18. The method of claim 1,further comprising removing the surface treatment layer.
 19. The methodof claim 1, wherein the surface comprises SiO₂, SiN, TiN, SiOC, SiON,Si, SiGe, Ge, or W.
 20. A surface treatment composition, comprising: atleast one siloxane compound in an amount of from about 0.1 wt % to about99.9 wt % of the surface treatment composition; and at least oneadditive comprising an acid having a pKa of at most 0 or an anhydridethereof in an amount of from about 0.1 wt % to about 10 wt % of thesurface treatment composition.
 21. The composition of claim 20, whereinthe at least one siloxane compound comprises a disiloxane, anoligosiloxane, a cyclosilxoane, or a polysiloxane.
 22. The compositionof claim 21, wherein the at least one siloxane compound compriseshexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane,1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane,1,1,3,3-tetra-n-octyldimethyldisiloxane,bis(nonafluorohexyl)tetramethyldisiloxane,1,3-bis(trifluoropropyl)tetramethyldisiloxane,1,3-di-n-butyltetramethyldisiloxane,1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane,1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane,hexaethyldisiloxane, hexavinyldisiloxane,1,1,1,3,3-pentamethyl-3-acetoxydisiloxane,1-allyl-1,1,3,3-tetramethyldisiloxane,1,3-bis(3-aminopropyl)tetramethyldisiloxane,1,3-bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,1,3-divinyltetraphenyldisiloxane, 1,3-divinyltetramethyldisiloxane,1,3-diallyltetrakis(trimethyl siloxy)disiloxane,1,3-diallyltetramethyldisiloxane, 1,3-diphenyltetrakis(dimethylsiloxy)disiloxane, (3-chloropropyl)pentamethyldisiloxane,1,3-divinyltetrakis(trimethyl siloxy)disiloxane,1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane,1,1,3,3-tetracyclopentyldichlorodisiloxane, vinylpentamethyldisiloxane,1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane,1,3-bis[(bicyclo[2.2.1]hept-2-enyl)ethyl]tetramethyldisiloxane,1,1,1-triethyl-3,3,3-trimethyldisiloxane,1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane,1,3-bis(chloromethyl)tetramethyldisiloxane,1,1,3,3-tetramethyl-1,3-diethoxydisiloxane,1,1,3,3-tetraphenyldimethyldisiloxane,methacryloxypentamethyldisiloxane, pentamethyldisiloxane,1,3-bis(3-chloropropyl)tetramethyldisiloxane,1,3-bis(4-hydroxybutyl)tetramethyldisiloxane,1,3-bis(triethoxysilylethyl)tetramethyldisiloxane,3-aminopropylpentamethyldisiloxane,1,3-bis(2-aminoethylaminomethyl)tetramethyldisiloxane,1,3-bis(3-carboxypropyl)tetramethyldisiloxane,1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane,1,3-diethynyltetramethyldisiloxane,n-butyl-1,1,3,3-tetramethyldisiloxane,1,3-dichlorotetraphenyldisiloxane, 1,3-dichlorotetramethyldisiloxane,1,3-di-t-butyldisiloxane, 1,3-dimethyltetramethoxydisiloxane,1,3-divinyltetraethoxydisiloxane,1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane,vinyl-1,1,3,3-tetramethyldisiloxane,platinum-[1,3-bis(cyclohexyl)imidazol-2-ylidene hexachlorodisiloxane,1,1,3,3-tetraisopropyl-1-chlorodisiloxane,1,1,1-trimethyl-3,3,3-triphenyldisiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane,3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethyltrisiloxane,hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane,1,5-diethoxyhexamethyltrisiloxane, 3-ethylheptamethyltrisiloxane,3-(tetrahydrofurfuryloxypropyl)heptamethyltrisiloxane,3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane,1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane,1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane,hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane,octachlorotrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane,(3,3,3-trifluoropropyl)methylcyclotrisiloxane,1,3,5-trivinyl-1,1,3,5,5-pentamethyltrisiloxane,1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane,3-(3-acetoxypropyl)heptamethyltrisiloxane,3-(m-pentadecylphenoxypropyl)heptamethyltrisiloxane,limonenyltrisiloxane,3-dodecylheptamethyltrisiloxane, 3-octylheptamethyltrisiloxane,1,3,5-triphenyltrimethylcyclotrisiloxane,1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane,1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane,1,5-dichlorohexamethyltrisiloxane, 3-triacontylheptamethyltrisiloxane,3-(3-hydroxypropyl)heptamethyltrisiloxane,hexamethylcyclomethylphosphonoxytrisiloxane,3-octadecylheptamethyltrisiloxane, furfuryloxytrisiloxane,tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane,a diphenyl siloxane-dimethylsiloxane copolymer,1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane,1,3-bis(trimethylsiloxy)-1,3-dimethyldisiloxane, adimethylsiloxane-[65-70%(60% propylene oxide/40% ethylene oxide)] blockcopolymer, bis(hydroxypropyl)tetramethyldisiloxane,tetra-n-propyltetramethylcyclotetrasiloxane,octaethylcyclotetrasiloxane, decamethyltetrasiloxane,dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane,tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane,polydimethylsiloxane, polyoctadecylmethylsiloxane, hexacosyl terminatedpolydimethylsiloxane, decamethylcyclopentasiloxane,poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy terminatedpolydimethylsiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane, ortriethylsiloxy terminated polydiethylsiloxane.
 23. The compositions ofclaim 20, wherein the at least one additive comprises methanesulfonicacid, trifluoromethanesulfonic acid, methanesulfonic anhydride,trifluoromethanesulfonic anhydride, acetic anhydride, perchloric acid,nitric acid, sulfuric acid, toluenesulfonic acid, dodecylbenzenesulfonicacid, hydroiodic acid, hydrobromic acid, hydrochloric acid, chloricacid, trichloroacetic acid, trifluoroacetic acid, or fluorosulfuricacid.
 24. The composition of claim 20, further comprising at least oneorganic solvent.
 25. The composition of claim 24, wherein the at leastone organic solvent is selected from the group consist of anhydrides,glycol ethers, glycol ether acetates, alkanes, aromatic hydrocarbons,sulfones, sulfoxides, ketones, aldehydes, esters, lactams, lactones,acetals, hemiacetals, alcohols, carboxylic acids, and ethers.
 26. Thecomposition of claim 24, wherein the at least one organic solventcomprises acetic anhydride, propylene glycol methyl ether acetate, aC₆-C₁₆ alkane, toluene, xylene, mesitylene, tetraethylene glycoldimethyl ether, propylene glycol dimethyl ether, ethylene glycoldimethyl ether, dipropylene glycol dimethyl ether, diethylene glycoldimethyl ether, dipropylene glycol dibutylether, n-dibutyl ether,dimethylsulfone, sulfolane, benzyl alcohol, t-butyl alcohol, t-amylalcohol, methyl ethyl ketone, acetic acid, or isobutyl methyl ketone.27. The composition of claim 24, wherein the at least one organicsolvent is from about 3 wt % to about 95 wt % of the surface treatmentcomposition.
 28. The composition of claim 20, wherein the composition issubstantially free of water.
 29. The composition of claim 20, whereinthe composition forms a surface treatment layer on a surface such thatthe surface treatment layer has a water contact angle of at least about50 degrees.
 30. A surface treatment composition, consisting of: at leastone siloxane compound in an amount of from about 0.1 wt % to about 99.9wt % of the surface treatment composition; at least one additivecomprising a compound selected from the group consisting of sulfonicacids and sulfonic anhydrides and being in an amount of from about 0.1wt % to about 10 wt % of the surface treatment composition; andoptionally, at least one organic solvent.
 31. An article, comprising: asemiconductor substrate; and a surface treatment composition supportedby the semiconductor substrate, the surface treatment compositioncomprising at least one siloxane compound and at least one additivecomprising an acid having a pKa of at most 0 or an anhydride thereof.32. The article of claim 31, wherein the semiconductor substrate is asilicon wafer, a copper wafer, a silicon dioxide wafer, a siliconnitride wafer, a silicon oxynitride wafer, a carbon doped silicon oxidewafer, a SiGe wafer, or a GaAs wafer.
 33. A kit, comprising: a firstcontainer comprising at least one siloxane compound; and a secondcontainer comprising at least one additive, the at least one additivecomprising an acid having a pKa of at most 0 or an anhydride thereof.